DIRECT SPECTROPHOTOMETRIC METHOD USING PICRIC ACID REAGENT

I. Outline
Free cyanide and weak-dissociable cyanide reacts with picric acid in solution to produce a bright
orange colour which can be measured using a spectrophotometer at 520 nm. The dissolved alkali
metal picrate is converted by cyanide into the coloured salt of isopurpuric acid and its
concentration is measured. The presence of a small amount of nickel in analysed solutions has a
positive effect on the overall performance of the method. The detection limit of this procedure is
0.26 mg/L. The method is suitable for the determination of weak acid dissociable cyanide. The
reduction of picric acid is effected by free cyanide only. Cyanide that is complexed with copper,
nickel, zinc or cadmium complexes can be liberated by metathesis with
diethylenetriaminepentaacetic acid (DTPA) or ethylenediaminetetraacetic acid (EDTA). Iron-
cyanide complexes, cobalt-cyanide complexes, gold-cyanide complexes, and silver-cyanide
complexes do not react leaving their complexed cyanide in tact.

The direct spectrophotometric method allows for the measurement of 20-300 µg cyanide in a
sample aliquot of up to 75 mL. Samples containing greater than 600 µg cyanide need to be
diluted.

II. Interferences
Thiocyanate, cyanate and thiosulfate ions have no adverse effects and can be tolerated at levels
2-
normally occurring in gold mill effluents. Sulfide is a source of interference, 0.1 mg S being
-
equivalent to 0.025 mg CN . If present, sulfide ions can be readily removed by the addition of lead
salts. However, it is unlikely that mill effluents would contain sulfide at levels large enough to
significantly interfere in the cyanide determination. Sulfide particles which contact the picric acid
reagent because of improper filtering of a gold bearing slurry will also cause the S2- interference.

The method requires close control of pH since it affects the colour intensity produced by the
cyanide-picric acid reaction. The most intense coloration results at pH 9.0-9.5. For maximum
sensitivity and good reproducibility of analytical results, the picric acid reagent solution should
therefore be buffered. In the present procedure a mixture of sodium tetraborate and carbonate as
well as DTPA itself serve this purpose. DTPA is preferred to EDTA due to more favourable values
of acid ionization constants and stability constants of some metal chelates.
III. Safety Precautions
Solutions of picric acid (trinitrophenol) are safe in ordinary laboratory use. However, in dry form
the acid and especially some of its salts have explosive properties. This requires that all picric
acid solutions be thoroughly washed down a sink with water. Spills must be carefully wiped up.
Picric acid has the tendency of staining the skin, and wearing protective hand gloves is therefore
recommended. Glass stained by picric acid is best washed with methanol or acetone.

IV. Reagents
Buffered Picric Acid Reagent
Dissolve 40g of diethylenetriaminepentaacetic acid and 16 g of NaOH in 900-950 mL of water.
Next dissolve, in the order given, 6 g of picric acid, 14 g of anhydrous sodium tetraborate or 27 g
Na2B4O7.10H2O and 8 g of anhydrous sodium carbonate. The pH of this solution is 8.7, and
would increase to 9.0 on a four-fold dilution. After reacting with cyanide the solution’s final pH
should be 9.2-9.3.
Nickel Solution, approximately 100 mg/L Ni.
Dissolve 0.22 g of NiSO4.6H2O and 1 g of NaCl in 500 mL of water.
Standard cyanide solution, 1000 mg/L cyanide
Dissolve 2.503 g of KCN and 1 g of KOH or NaOH in water and dilute to 1 litre. Make further
dilutions as necessary for the preparation of the calibrating working standard.

V. Procedure
Transfer into a 150 mL beaker a suitable volume of samples solution which contains 1-300 µg of
cyanide. Add 1 mL of nickel solution, swirl, and dilute with water to about 70 mL. Measure about
70 mL of water in another beaker, add 1 mL of nickel solution and carry through the procedure as
the reagent blank. Add 25.0 mL of buffered picric acid reagent to each beaker and heat for 35
minutes on a hotplate with surface temperature adjusted to 160 0C, without allowing to boil. If a
white precipitate of calcium carbonate forms add 0.1-0.2 g of EDTA disodium salt. Cool the
solutions to room temperature, transfer to 100 mL volumetric flasks and dilute to volume.
Measure the absorbance of the solutions more deeply coloured than the reagent blank at 520 nm
using the reagent blank as the reference. The absorbance of the reagent blank usually varies
between 0.006 – 0.009 (520 nm, slit width 0.03 mm, 1 cm path cell).

VI. Calibration
Into 150 mL beakers pipette aliquots of the standard cyanide solution containing 25, 50, 100, 200
and 300 µg cyanide. Add 1 mL nickel solution to each of them, mix, and dilute to about 70 mL
with water. Add 25.0 mL of buffered picric acid reagent and proceed as described under
“procedure”. Always measure absorbance against the respective reagent blank.
Plot the absorbance readings vs. µg cyanide added in the aliquots of the standard cyanide
solution, and construct the calibration graph.

VII. Calculation
Convert the absorbance reading of the aqueous solution or the extract into micrograms of
cyanide using the calibration graph. Calculate the cyanide concentration in the original samples
solution as follows:

- -
mg/L CN = A/B where : A = µg CN found from the graph and B = volume, in mL, of the sample
solution used for the analysis.

VIII. Reference
Iamarino, P.F. (1989) The direct spectrophotometric determination of cyanide with picric acid
reagent. JRGRL June 1 1989. INCO Ltd. (based on V.J.Zatka method (JRGRL, November 1980
which was a modification of the method of D.J. Barkley and J.C. Ingles, Report 221, CANMET,
(February 1970).